Classifications

• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/425—Cellulose series
  • D04H1/4258—Regenerated cellulose series
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
  • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
  • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
  • D04H1/43838—Ultrafine fibres, e.g. microfibres
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
  • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
  • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
  • D06M13/2243—Mono-, di-, or triglycerides
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
  • D06M2101/02—Natural fibres, other than mineral fibres
  • D06M2101/04—Vegetal fibres
  • D06M2101/06—Vegetal fibres cellulosic

Definitions

• the present disclosure is directed to oil-infused bacterial nanocellulose materials for use as a fabrics and textiles and methods of manufacturing the same.
• the leather industry is a greater than 100-billion-dollar industry that produces a unique textile material with desired physical and handling properties (when compared to other textile materials) through the mechanical and chemical treatment of animal hides and skins.
• the leather industry has grown at a rate that the demand for leather products outpaces the meat industry.
• Demand for animal meat is rising at a rate of approximately 3 percent, which closely reflects the growth rate of the human population, while demand for leather products is growing at a rate of 4-7%. Due to this increase of demand, leather material providers have had to look to other livestock to meet the growing demand for pelt material.
• Cellulose of various origins has been proven to be a versatile biomaterial for multiple applications. Synthesized by just about every type of plant and a select number of microorganisms, such as certain yeasts and bacteria, it is an all-natural, renewable,
• biocompatible, and degradable polymer used in a wide variety of applications including paper products, food, electronics, drug coatings, and bandages.
• Cellulose formed from bacteria i.e., bacterial nanocellulose (BNC)
• BNC bacterial nanocellulose
• Cellulose derived from bacteria forms a porous three-dimensional network of cellulose nanofibers that under certain conditions can simulate some of the physical and mechanical properties of natural hides (e.g., leather), such as grain texture and flexibility.
• natural hides e.g., leather
• an oil-infused bacterial nanocellulose (BNC) material including a porous body having a three-dimensional network of bacterial nanocellulose fibers, where the nanocellulose fiber network defines a plurality of interconnected pores, and an oil infused within the plurality of pores.
• the oil-infused BNC material comprises a porous body of never-dried bacterial nanocellulose.
• the porous body is pure BNC material.
• the porous body is fully dehydrated.
• the nanocellulose fibers have a crystallinity as measured by x-ray diffraction (XRD) of at least 65%.
• the porous body has a cellulose content in the range of about 20 mg/cm 2 to about 30 mg/cm 2 .
• the oil -infused BNC material has a thickness in the range of about 1 mm to about 10 mm.
• the oil comprises at least 70% by weight of the total weight of the oil-infused BNC material. In still other embodiments, the oil comprises about 70% to about 95% by weight of the total weight of the oil-infused BNC material.
• the oil-infused BNC material has a tensile strength in the range of about 275 N/cm 2 to about 2100 N/cm 2 . According to further embodiments, the oil-infused BNC material has a tensile strength in the range of about 275 N/cm 2 to about 2100 N/cm 2 . According to further embodiments, the oil-infused BNC material has a tensile strength in the range of about 275 N/cm 2 to about 2100 N/cm 2 . According to further
• the oil-infused BNC material has a tensile load at failure value in the range of about 50 N to about 150 N. According to still further embodiments, the oil-infused BNC material has a stitch pullout failure load in the range of about 5 N to about 40 N.
• the oil-infused BNC material further includes one or more dyes or sealing agents.
• the textile or fabric material comprises a single sheet of oil-infused BNC.
• the textile material comprises a plurality of sheets of oil-infused BNC; in other words, a multi-layer textile material of oil-infused BNC.
• the sheet can comprise a plurality of oil-infused BNC strips, strands, or fibers, or combinations thereof, that are woven or knitted or braided, or other known methods of interlacing or interconnection that are commonly known to those of skill in the art.
• the oil-infused sheet is a continuous, uniform, monolithic structure.
• the present disclosure additionally describes a method of preparing an oil- infused bacterial nanocellulose (BNC) material comprising the steps of:
• an oil infusion fluid including an oil so as entrap the oil in the pores of the porous body so as to form an oil-infused BNC material.
• the fermentation step includes fermenting at a temperature in the range of about 30°C +/- 2°C. According to additional embodiments, the fermentation step includes fermenting for a time period in the range of about 5 days to about 30 days. In certain embodiments, fermenting is done in at a pH in the range of about 4.1 to about 4.6. In certain embodiments, the method can include purifying the porous body after fermentation.
• dehydrating the porous body comprises using a solvent including one or more water-miscible organic solvents.
• the solvent is heated to boiling.
• the weight to volume ratio in mg/ml of the nanocellulose fibers to the solvent can be in the range of about 15: 1 to about 8: 1.
• the oil infusion fluid is heated during the infusion step.
• the weight to volume ratio in mg/ml of the nanocellulose fibers to the oil infusion fluid is in the range of about 1 : 1 to about 1 : 10.
• the oil infusion fluid includes an emulsifier.
• the emulsifier includes a water-miscible organic solvent.
• the oil infusion fluid has an oil to emulsifier ratio by volume in the range of about 90: 10 to about 10:90.
• the present method can further include a step of dying the oil-infused BNC material.
• Figs. 1A-C are photographic images of specimens (#1-10, Fig. 1A, #11-20, Fig. IB, and #21-30 Fig. 1C) as used in the tensile strength test described below; and,
• Figs. 2A-C are photographic images of specimens (#1-10, Fig. 2A, #11-20, Fig. 2B, and #21-30 Fig. 2C) as used in the suture pullout test described below.
• an oil-infused, bacterial nanocellulose (BNC) material is described, as well as methods for forming the same.
• One type of bacterial cellulose that is particularly suited for the present disclosure is synthesized by the bacteria Acetobacter xylinum (reclassified as Gluconacetobacter and/or Komagataeibacter).
• the cellulose produced by this bacteria is characterized by a highly crystalline three-dimensional network consisting of pure cellulose nanofibers (i.e., cellulose fibers having a cross-sectional dimension in the nanometer range) that is stabilized by inter and intra hydrogen bonds.
• Such a fibrillar network displays high strength, flexibility, and large nanofiber surface area.
• the cellulose nanofibers define an interconnecting heterogeneous pore network with high void space (i.e., porosity) that allows for the entrapment and retention of secondary filler materials. These properties make this material ideally suited as a replacement for natural leather products, which are formed from three-dimensional networks of the protein collagen.
• the bacterial nanocellulose is“pure bacterial nanocellulose” in that it is cellulose synthesized solely from bacterial sources. In other words, there are no other types of microbes, such as yeast for example, that contribute to the cellulose synthesis process or to the overall structure and appearance of the final product.
• the pure bacterial nanocellulose is synthesized solely from a vinegar bacteria source, for example,
• the bacterial nanocellulose fibers have a crystallinity, when measured by XRD, of at least 65%, preferably at least 80%, up to an including at least 95%.
• the porous body has a pore volume (i.e., porosity) of at least 75%, at least 80%, or at least 90%.
• the porous body has a cellulose content in the range of about 15 mg/cm 2 to about 40 mg/cm 2 , such as, for example, a range of about 20 mg/cm 2 to about 30 mg/cm 2 . Cellulose content as measured herein will be described further below.
• an oil-infused BNC material including a porous body of bacterial nanocellulose fibers and an oil component, where the oil component is entrapped within the pore network of the porous body.
• Oil as used herein, includes mineral oil and waxes, and natural oils, fats, and waxes derived from plants and animals, as well as synthetic derivatives thereof. Oils and waxes known to be useful in the fatliquoring processes of animal hides are considered as suitable within the present disclosure.
• the oil component can include compositions of pure oil, as well as a composition wherein the majority portion by weight includes an oil, or combination or mixture of oils.
• the oil component can include a minority portion of an emulsifying agent to assist the penetration of the oil into the porous network of the porous body.
• Suitable emulsifying agents can include, for example, water-miscible organic solvents, such as will be described in more detail below.
• Mineral Oils and Waxes are a byproduct obtained from crude oil and typically include mixtures of many alkanes and cycloalkanes, which are separated by distillation. Mineral oils are typically immiscible with water and can provide some degree of waterproof properties. They can be available in a variety of viscosities and typically have a density lighter than water. Mineral waxes can include, for example, paraffin wax, lignite wax, and ceresine wax. This list is not meant to be exclusive.
• oils and fats in animals, fish and plants are fatty acid glycerides. These fatty acids are mostly water insoluble and range from very fluid oily liquids to greasy pastes and hard waxy materials.
• Fatty acids may be classified as saturated or unsaturated.
• Saturated fatty acids are usually more viscous or solid, do not darken with exposure to sunlight, and can typically resist oxidation upon exposure to air and moisture.
• Unsaturated fatty acids are more fluid (less viscous), darken with sunlight, and can become sticky or gummy on oxidation by air.
• Most naturally occurring fatty acids have an even number of C atoms.
• Shorter chain saturated fatty acids such as C-6, C-8, and C-10, are found in coconut and palm oils, milk fat and other softer oils.
• C-12, lauric acid is found in sperm oil.
• Saturated fatty acids of C-16 and C-18 are common to animal fats and many vegetable oils.
• the C-24 and C-25 category are found in waxes, such as carnauba wax and beeswax.
• the unsaturated fatty acids, with more than 1 double bond can be classified as drying oils such as linseed or cottonseed oils. Some contain -OH groups such as lanopalmic acid (C-16 hydroxy, saturated) found in wool fat (or wool grease) and ricinoleic acid (C-18 hydroxy, unsaturated) found in castor oil.
• drying oils such as linseed or cottonseed oils.
• Some contain -OH groups such as lanopalmic acid (C-16 hydroxy, saturated) found in wool fat (or wool grease) and ricinoleic acid (C-18 hydroxy, unsaturated) found in castor oil.
• Exemplary animal oils and fats can include: cod liver oil, herring oil, salmon oil, sardine oil, japanese fish oil, menhaden oil, whale oil (e.g., sperm oil), beef tallow, mutton tallow, wool fat and grease, stearine , stearic acid, milk fat (or butterfat), and neatsfoot oil.
• Exemplary vegetable oils can include: coconut oil, cottonseed oil, olive oil, palm oil, palm kernel oil, castor oil, linseed oil and soybean oil.
• Exemplary natural waxes can include carnauba wax, candelilla wax, and beeswax.
• the porous body is fully dehydrated.
• “fully dehydrated” means that the porous body contains less than 5% by weight of free water molecules, and can contain, in certain embodiments, less than 1% by weight of free water molecules. It should be appreciated that some degree of hydrogen bonding occurs in and between the nanocellulose polymer chains of the porous body, such that a percentage of water molecules can be bound via hydrogen bonding in the polymer network, and thus are not“free” as that term is understood in the art.
• the porous body is “never dried” from synthesis to its final state.
• “never dried” when referring to the porous body means that at least 80%, preferably 90%, and most preferably 95% or more of the total volume of void space defined by the porous network of bacterial nanocellulose fibers is continuously occupied with a liquid, from fermentation through to the final oil-infused BNC material embodiments described herein.
• “never-dried” refers to the porous body or the oil-infused BNC material having 95% or greater of the total volume of void space being continuously occupied with a liquid from the start of fermentation.
• Dehydration is directed to the processes of water removal, which can under certain circumstances, include drying. Drying is directed to processes where liquid (of any type) is removed from the pores of the porous body and the pore spaces become occupied by a gas or vapor (e.g., air or CO2).
• a gas or vapor e.g., air or CO2.
• the infusion of oils, fats and waxes into a porous body of bacterial nanocelluose is not as efficiently accomplished using traditional fat liquoring techniques for animal hides.
• Oil-infusion of a porous body of never-dried bacterial nanocellulose can create a completely natural, environmentally degradable, product with leather-like properties, durability, and appearance, with the additional benefit of eliminating the use of aggressive chemical processing, animal slaughter, and environmental contamination.
• the oil-infused BNC material can have a thickness in the range of about 1 mm to about 20mm, for example in the range of about 1 mm to about 10mm, for example in the range of about 1mm to about 5mm.
• the oil comprises at least 70% by weight of the total weight of the oil-infused BNC material, up to and including at least about 95%, for example in the range of about 75% to about 95%, from about 75% to about 90%, about 80% to about 95%, about 80% to about 90%, from about 80% to 85%, from about 85% to about 90%, and any subcombination of the ranges here disclosed.
• the oil-infused BNC material has a tensile strength in the range of about 275 N/cm 2 to about 2100 N/cm 2 . According to further embodiments, the oil-infused BNC material has a tensile load at failure value of about 50 N to about 150 N. According to still further embodiments, the oil-infused BNC material has a stitch pullout failure load of about 5 N to about 40 N.
• the textile or fabric material comprises a single sheet of oil-infused BNC.
• the textile material comprises a plurality of sheets of oil-infused BNC; in other words, a multi-layer textile material of oil-infused BNC.
• the sheet can comprise a plurality of oil-infused BNC strips, strands, or fibers or combinations thereof, that are woven or knitted or braided, or other known methods of interlacing or interconnection that are commonly known to those of skill in the art.
• the oil-infused sheet is a continuous, uniform, monolithic structure.
• methods of preparing an oil-infused BNC material include
• bacterial cells in this case Gluconacetobacter xylinus ( Acetobacter xylinum) are cultured/incubated in a bioreactor containing a liquid nutrient medium.
• liquid nutrient medium can affect the resultant quality and quantity of cellulose produced from the cultured bacteria.
• Culture media for the growth of the cellulose typically includes a sugar source and a nitrogen source, as well as additional nutrient additives.
• Suitable sugar sources can include both monosaccharides such as glucose, fructose, and galactose, as well as disaccharides, such as sucrose and maltose, and any combinations thereof.
• Suitable nitrogen sources can include ammonium salts and amino acids.
• Corn steep liquor is a preferred culture media component that provides both the nitrogen source as well as additional desirable additives including vitamins and minerals.
• Suitable nutrient additives can additionally include, for example, sodium phosphate, magnesium sulfate, citric acid, and acetic acid.
• Increasing the total sugar content of the media can result in higher quantity of cellulose produced. Modifying the type of sugars added, or where multiple sugars are added, their respective ratios, can also cause changes to the resultant cellulose yields.
• a sugar source blend including glucose and fructose can have, according to one embodiment, a higher glucose to fructose ratio, which can result in a lower strength cellulose material.
• a higher fructose to glucose ratio can result in a cellulose material exhibiting higher strength.
• increasing the amount of the nitrogen source can increase the quantity of cellulose produced.
• the culture media is kept at an acidic pH, for example at around 4.0-4.5. Increasing the media pH above 5.0 or greater can, in certain situations, result in reduced bacterial cell growth.
• the temperature of the culture media is kept above room temperature, for example in the range of about greater than 25°C to about 35°C. In a preferred embodiment, the culture media is in the range of about 30°C. Adjustments to the incubation temperature can in certain instances affect the growth of the cellulose materials.
• Increasing the incubation temperature can, according to one embodiment, increase the amount of cellulose yielded. Alternatively, lowering the incubation temperature can decrease the amount of cellulose material yielded. According to one embodiment, the bacterial cells are cultured for approximately 1-4 days prior to beginning the fermentation process.
• the fermentation process begins.
• the cultured media is typically poured into bioreactor trays to begin the fermentation process.
• the higher the amount of bacterial cells in the culture media results in a higher quantity of cellulose produced.
• the fill weight of the culture media is in the range of about 1.5L to about 15L, for example in the range of about 4L to about 8L, or about 5L to about 10L.
• the fermentation process is typically carried out in a shallow bioreactor with a lid which reduces evaporation.
• Such systems are able to provide oxygen-limiting conditions that help ensure formation of a uniform cellulose pellicle.
• Dimensions of the bioreactor can vary depending on the desired shape, size, thickness and yield of the cellulose being synthesized.
• the fermentation process occurs at around 30 ⁇ 2°C in an acidic environment having a pH of about 4.1 to about 4.6 under static conditions for about 5 days to 30 days.
• the fermentation step can occur in the temperature range of about 20°C to about 40°C, such as, for example, 20°C to 30°C, 30°C to 40°C, 25°C to 35°C, 28°C to 32°C, 28°C to 30°C, and 30°C to 32°C.
• fermentation occurs in the range of 28°C to 32°C, and more particularly preferred at about 30°C.
• the fermentation can occur in at an acidic pH, for example in the range of about 3.3 to about 7.0, such as for example in the range of about 3.5 to about 6.0, or 4.0 to about 5.0.
• the fermentation occurs at a pH range of about 4.1 to about 4.6.
• the time period for fermentation can vary. According to embodiments of the present disclosure, fermentation can occur from about 5 days to about 60 days depending upon the desired growth of the cellulose pellicle. For example, fermentation can occur from about 5 days to about 10 days, from about 5 days to about 30 days, from about 10 days to about 50 days, from about 10 days to about 25 days, from about 20 days to about 60 days, from about 20 days to about 50 days, and from about 20 days to about 30 days, as well combinations of ranges falling within the ranges stated herein. According to certain embodiments, a longer fermentation results in a higher amount of cellulose produced, while alternatively, a reduced fermentation time results in a lower amount of cellulose produced. Depending on the desired thickness and/or cellulose yield, the fermentation can be stopped, at which point the cellulose pellicle (i.e, porous body of cellulose) can be harvested from the fermentation tray bioreactor.
• the cellulose pellicle i.e, porous body of cellulose
• the porous body of nanocellulose can undergo a purification process where the porous body is rendered free of microbes; i.e., the porous body is chemically treated to remove bacterial by-products and residual media.
• a caustic solution preferably sodium hydroxide, at a preferable concentration in the range of about 0.1M to 4M, is used to remove any viable organisms and pyrogens (endotoxins) produced during fermentation from the porous body. Processing times in sodium hydroxide of about 1 to about 12 hours have been studied in conjunction with temperature variations of about 30°C to about 100°C to optimize the process.
• a preferred or recommended temperature processing occurs at or near 70°C.
• the treated porous body can be rinsed with filtered water to reduce microbial contamination (bioburden) and achieve a neutral pH.
• the porous body can be treated with a dilute acetic acid solution to neutralize remaining sodium hydroxide.
• the porous body after harvesting, can undergo one or more mechanical pressings (either prior to or after purification where utilized) to remove excess water, reduce the overall thickness, and increase the cellulose density of the porous body.
• the porous body may be additionally processed through thermal modification via freezing and dehydration at a range of about -5°C to -80°C for about 1 - 30 days, which can further decrease thickness and increase cellulose density.
• the porous body after harvesting of the cellulose pellicle, most frequently after an initial mechanical press of the porous body to physically remove a bulk quantity of water and compress the thickness, the porous body can be processed with a water-miscible organic solvent for one to up to several cycles to further dehydrate the porous body. If desired the porous body can undergo further mechanical pressing after completion of the solvent exchange dehydration step.
• Exemplary water-miscible organic solvents can include, for example, acetaldehyde, acetic acid, acetone, acetonitrile, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2- butoxyethanol, butyric acid, diethanolamine, diethylenetriamine, dimethylformamide, dimethoxy ethane, dimethyl sulfoxide, 1 ,4-dioxane, ethanol, ethylamine, ethylene glycol, formic acid, furfuryl alcohol, glycerol, methanol, methyl diethanolamine, methyl isocyanide, N-methyl- 2-pyrrolidone, 1-propanol, 1,3 -propanediol, 1,5-pentanediol, 2-propanol, propanoic acid, propylene glycol, pyridine, tetrahydrofuran, and triethylene glycol.
• the porous body is immersed in the solvent.
• the porous body can undergo one or more solvent exchanges during processing to increase dehydration of the porous body.
• the porous body can be immersed in one, two, three, four, five, up to about 10 solvent exchanges during solvent dehydration.
• the solvent can be heated substantially near, or at, its boiling point during the solvent dehydration process. In a preferred embodiment, the solvent is in a boiling state during the entire dehydration process.
• the weight to volume (mg/mL) ratio of the cellulose nanofibers to solvent can be in the range of 15: 1 or less, 12: 1 or less, 10: 1 or less, or 8: 1 or less.
• the solvent is mechanically agitated during the process, for example with a magnetic stirring device or other known processes.
• the porous body can once again undergo one or more mechanical pressings to remove excess solvent or achieve a desired thickness.
• the porous body can be further dehydrated by critical point drying utilizing supercritical carbon dioxide.
• critical point drying the wet porous body (either having water or solvent, or both entrapped within the pores) is loaded onto a holder, sandwiched between stainless steel mesh plates, and then soaked in a chamber containing supercritical carbon dioxide under pressure.
• the holder is designed to allow the CO2 to circulate through the porous network while mesh plates stabilize the porous body to prevent it from deforming during the drying process.
• the temperature in the chamber is increased above the critical temperature for carbon dioxide so that the CO2 forms a supercritical fluid/gas. Due to the fact that no surface tension exists during such transition, the resulting product is a dehydrated and dried porous body which maintains its shape, thickness and 3-D nanostructure. According to the present disclosure, the resultant porous body can be referred to as“critically dried.”
• the porous body after dehydration of the porous body via either solvent or supercritical drying, or both, can be subjected to one or more oil infusion steps to allow the oil component to penetrate the porous body and become entrapped within the pore network so as to form an oil-infused BNC material.
• the porous body is completely submerged in a container containing an oil infusion fluid including the oil.
• the ratio in weight to volume (mg/ml) of nanocellulose fibers to oil infusion fluid is less than about 15: 1 to about 1 : 1, such as for example, 12: 1, 10: 1, 8: 1, 5: 1, 4: 1, 3: 1, 2: 1, and combinations and subranges of each of the preceding ratios.
• the oil infusion fluid can be applied and pressed into the porous body, such as for example, with the use of rollers, brushers, or pads.
• the oil infusion fluid includes only the oil component.
• the oil infusion fluid can include the oil component combined with an emulsifier to promote the infusion of the oil component into the porous body.
• oil infusion fluid having an emulsifier and an oil can increase the total amount of oil entrapped in the final oil-infused BNC material.
• Suitable emulsifying agents can include, for example, the water-miscible organic solvents previously disclosed as suitable for the solvent dehydration process.
• the oil infusion fluid can be prepared to have an oil to emulsifier ratio by volume in the range of about 90: 10 to about 10:90 and any subrange therein, for example 80:20, 70:30, 60:40, 50:50, 40:60, 30:70, and 20:80.
• a higher ratio of oil to emulsifier can result in a higher concentration of entrapped oil in the final oil-infused BNC material.
• the oil infusion fluid can be heated during the oil-infusion process.
• One benefit to heating the oil infusion fluid is to ensure that any of the heavier oil components that have a melting point higher than ambient temperature can melt, or at least have a reduced viscosity to assist the formation of a suitable emulsion.
• the oil infusion fluid is heated to boiling.
• the oil infusion fluid is constantly agitated or otherwise mixed during the infusion process. Agitation is beneficial to ensuring homogeneity within the oil infusion fluid, such as for example, where one or more oils are present in the oil component, or where the oil component is combined with an emulsifier. Agitation can further promote the penetration of the oil infusion fluid into the porous network of the porous body.
• the oil-infused BNC material can undergo further processing.
• the oil-infused BNC material can be dried to remove any residual water or solvents still remaining within the pore network.
• the drying can be done in an air oven and can further include tumble drying.
• the oil-infused BNC can be further processed to impart aesthetic qualities such as dying and or surface treatments to alter the texture of the surface or to add a design or pattern to the surface.
• the oil-infused BNC material can be mechanically pressed to reach a final desired thickness or weight, or to remove any excess oil from the final BNC material.
• the oil-infused BNC material can undergo a sealing or finishing step that aids in retaining the oil within the pore network.
• a strain of Gluconacetobacter ( Komagataeibacter ) was cultured in sucrose and corn-steep liquor based media (including an autoclave step) and 7.2L (4.2 L of media + 3L of inoculum) was poured into a stationary reactor tray for fermentation. Fermentation lasted for 26 days at a temperature of approximately 31°C at a pH in the range of 4.1-4.6.
• the pellicle had an average thickness of approximately 5cm and weighed 5.605kg.
• the porous body i.e., pellicle formed at the surface had the aesthetic and tactile properties observed in natural leather hides.
• the porous body was purified by washing with 1-6% aqueous NaOH and bleached with 0.1-1% H2O2, followed by soaking in distilled/purified water to obtain a neutral pH.
• the porous body was mechanically pressed to desired thicknesses.
• the weight of the water infused porous body after purification and pressing was 230.96g and the porous body had an average cellulose content of approximately 22.9mg/cm 2 .
• Cellulose content was measured by taking a sample of the wet porous body with a known area and air drying for approximately 12hrs at 55°C which resulted in a porous body that theoretically includes only the nanocellulose fibers. In other words, the total weight of the dried porous body was completely due to the nanocellulose fibers. Cellulose content was measured by dividing the weight of the dried sample by its area.
• the wet pressed porous body was then cut into 45 strips, each approximately 5cm x 5cm and each having a cellulose content of approximately 575mg (i.e., 22.9mg/cm 2 ).
• the wet strips were measured for thickness at each of their four corners and their average wet thickness was recorded in the table below.
• the strips were then randomly divided into 3 groups of 10 samples each and were processed through a solvent extraction step and an oil infusion step.
• the solvent extraction for the samples was the same and included a multistep extraction using boiling ethyl alcohol [ETOH] (approx. 70°C) having 99% purity.
• the samples were placed in a flask with a mechanical stirrer operating at approximately 200rpm and containing about 1500mL of ETOH for about 2 hours to 24 hours.
• a second extraction step was done separately with each of the 10 samples from Group 1, 2, and 3, respectively with 500mL of boiling ETOH, including a stirrer at 200rpm for about 2 hours to 24 hours.
• Group 1 samples (samples 1-10) were placed in a flask containing a heated oil infusion fluid at about 70°C under constant mixing.
• the oil infusion fluid contained 250mL of ETOH as an emulsifier and 250ml of unrefined coconut oil (a 50:50 emulsifier/oil ratio).
• Group 2 samples (samples 11 -20) were placed in a flask containing a heated oil infusion fluid at about 70°C under constant mixing.
• the oil infusion fluid contained 350mL of ETOH as an emulsifier and 150ml of unrefined coconut oil (a 70:30 emulsifier/oil ratio).
• Example 3 samples were placed in a flask containing a heated oil infusion fluid at about 70°C under constant mixing.
• the oil infusion fluid contained 150mL of ETOH as an emulsifier and 350ml of unrefined coconut oil (a 30:70 emulsifier/oil ratio).
• Each group of samples underwent oil- infusion for approximately 2 hours. After the oil infusion process was complete, the samples were weighed to record their weight, shown in the table below as“Infusion wt.” The samples were air dried for approximately 24 hours in a fume hood and their dry weight and average thickness was recorded.
• the oil weight and oil percent of the final dried product were calculated by subtracting the known cellulose weight of the sample (approximately 575mg) from the total dry weight of the oil-infused BNC material.
• Tables for Groups 1-3 showing the measured weights and thicknesses of the samples from the solvent wash stage through to drying.

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• Chemical Kinetics & Catalysis (AREA)
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• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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